Monovalent cation permselective membranes (MCPMs) manifest remarkable effectiveness and potential in lithium extraction whereas facing the challenge to achieve high permselectivity and high Li+ permeability simultaneously. In this work, Zn-TCPP, a kind of two-dimensional nanosheet with abundant negative charges, was successfully synthesized via surfactant-assisted method and introduced into surface cross-linked SPES membrane to fabricate MCPMs. The physicochemical properties, electrochemical properties and Li+/Mg2+ separation performance of resulted MCPMs were systematically estimated. As ions passing through the membrane, dense PVA/GA crosslinked layer separated Li+ and Mg2+ by pore-size sieving effect. Afterwards, uniformly distributed Zn-TCPP nanosheets with rich negative charges and physically adsorbed water molecules elevated the charge density and water content in the membrane and thus expedited Li+ transporting. Therefore, high Li+/Mg2+ permselectivity (PMg2+Li+= 8.99) and Li+ permeation flux (JLi+= 9.12 × 10−9 mol cm−2∙s−1) were obtained. Furthermore, membrane surface resistance was reduced from 108.99 Ω cm2 to 24.12 Ω∙cm2. This study points out the feasibility of the new method for accelerating monovalent ion transport and alleviating the restriction between ion permeation and permselectivity in selective ion exchange membranes.